US2727032A

US2727032A - Cobaltiferous monoazo-dyestuffs

Info

Publication number: US2727032A
Application number: US302626A
Authority: US
Inventors: Buehler Arthur; Zickendraht Christian
Original assignee: Ciba AG
Current assignee: BASF Schweiz AG
Priority date: 1951-08-07
Filing date: 1952-08-04
Publication date: 1955-12-13
Anticipated expiration: 1972-12-13

Description

United States Patent 2,727,032 COBALTIFEROUS MONOAZO-DYESTUFFS Arthur Buehler, Rheinfelden, and Christian Zickendraht, Binningen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application August 4, 1952, Serial No. 302,626

Claims priority, application Switzerland August 7, 1951 17 Claims. (Cl. 260-147) According to this invention .valuable new cobaltiferous azo-dyestutfs are made by treating a monoazo-dyestufi free from sulfonic acid and carboxylic acid groups and corresponding to the general formula in which R1 represents a benzene radical bound to the azo linkage in ortho-position relatively to the hydroxyl group, and R2 represents the radical of a coupling component containing an aromatic radical and capable of coupling in a position vicinal to a hydroxyl group, and in which one of the radicals R1 and R2 contains an aromatically bound methyl sulfone group with an agent yielding cobalt in such manner that the resulting cobaltiferous dyestuff contains less than one atom of cobalt in complex union per molecule of monoazo-dyestuff.

The monoazo-dystufis corresponding to the above general formula and serving as starting materials in the present process can be made from diazoand couplingcomponents which are free from sulfonic acid and carboxylic acid groups and contain an aromatically bound methyl-sulfone group, which may be present in the coupling-component or in the diazo-component, but advantageously in the latter component. Such dyestutt components containing an aromatically bound methyl sulfone group are obtained by methods in themselves known by methylating the appropriate sulfinic acids, for example, with dimethylsulfate, or by oxidizing the appropriate aromatic methyl thioethers. 'Thus, the methyl-sulfonylorthoaminophenols valuable in the present process are obtainable from ortho-nitro-chlorobenzene sulfonic acid chlorides by first converting the latter by mild reduction with sodium sulfite into the corresponding sulfinic acids, methylating the latter, then replacing thechlorine atom by a hydroxyl group by means of caustic alkali, and converting the nitro group into an amino group, for example, by reduction with sodium sulfide.

As examples of diazo compounds coming into consideration there may be mentioned those obtained by diazotizing the following amines: H p

(a) Amines containing methyl sulfone groups such as 6-nitroor 6-chloro-2-amino-1hydroxybenzene-4-methyl sulfone, 4-nitroor 4-chloro 2-amino-l-hydroxybenzeneor 6-methyl sulfone, 2-arnino-l-hydroxybenzene-4:6- di-(methyl sulfone) and {especially Z-amino-I-hydroxybenzene-4- or 5-methyl sulfone, and also ([2) Compounds containing no methyl sulfone groups, (which are therefore coupled only with azo components containing methyl sulfone groups), such as 4-nitro-, 4-chloro-, 4-methoxyor 4-methyl-2-amino-1-hydroxybenzene, 4:6-dichloro-2-amino-l-hydroxybenzene, S-nitro- 2 amino-l-hydroxybenzene, 4-nitro-6-ch1oro-2-amino-1- hydroxybenzene, 3:4:'6-tricl1loro-2-aminol-hydroxybenzene, 3-amino-4-hydroxy-acetophenone, 4-nitro-6-acetylamino Z-amino-l-hydroxybenzene, 6-nitro-4-acetylamino- Z-amino-l-hydroxybenzene, 4-chloro-2-amino-1-hydroxybenzene5-'- or 6-sulfonic acid amide, 6-nitro2-amino-1- hydroxybenzenei-sulfonic acid amide, 2-amino-1-hydroxybenzene-4- or 5-sulfonic acid amide and the corresponding substituted sulfonic acid amides such as 2-amino- 1hydroxybenzene-4-sulfonic acid methylamide, ethylamide, n-butylamide, dimethylamide, diethylamide or phenylamide.

As coupling components to be used for preparing the monoazo-dyestuifs serving as starting materials in the present process, there come into consideration those which contain an aromatic radical and owe their coupling capacity to a phenolic hydroxy group or a keto methylene group. Coupling compounds which are free from methylsulfone groups or which contain up to 2 methylsulfone groups may be used. Among the coupling components free from methyl sulfone groups, which are to be coupled only with the diazo compounds of the hydroxy-amines mentioned above under (a), there may be mentioned, for example, hydroxyquinolines; phenols such as para-cresol or resorcinol; naphthols such as 4-methyl-1-hydroxynaphthalene, S-chloroor 5 :S-dichloro-l-hydroxynaphthalene, Z-hydroxy-uaphthalene, 6-methoxyor 6-bromo-2- hydroxynaphthalene, 1-acetyl-, l-n-butyrylor l-benzoylamino -7- hydroxynaphthalene, Z-hydroxynaphthalene-fisulfonic acid amide or the corresponding N-methylamide or N-phenylamide; acylacetic acid arylamides, such as acetoacetic acid phenylamide, aceto acetic acid orthochloranilide, l-acetoacetylaminobenzene-3- or 4-sulfonic acid amide; pyrazolones such as 5-pyrazolone-3-carboxylic acid anilide, l-phenyl 3 methyl 5 pyrazolone, 1phenyl-3methyl-S-pyrazolone-3- or 4'-sulfonic acid amide, 1phenyl-3-methyl-S-pyrazolone-4-sulfonic acid- N-methylamide, or N-phenylamide, l-phenyl-S-pyrazolone-3-carboxylic acid amide, i-phenyl-S-pyrazolone-B- carboxylic acid-N-butylamide or N-phenylamide, and also 1-(2'- or 3'- or 4'-chlorophenyl)3-methyl-5-pyrazolone. Coupling components containing methyl sulfone groups, which can be coupled either with the diazo compounds obtained from the hydroxy amines mentioned under (a) above or those mentioned under (b) above, are obtainable, for example, from aminobenzene methyl sulfones by condensing the latter with diketene or B-ketocarboxylic acid esters to form the corresponding aceto or acylacetic acid anilides, or by converting the amino, group of the aminobenzene methyl sulfones by methods in themselves known into a hydrazine group, and condensing the resulting products with fi-keto-carboxylic acid esters to form l-aryl-S-pyrazolones. It is also possible to convert O-acyl-sulfonyl compounds of naphthol sulfonic acids into the corresponding sulfonic acid chlorides and sulfinic acids, then to methylate the latter and finally to hydrolyze the O-acyl groups, Especially suitable coupling components of this kind are l-hydroxynaphthalene-3- or 4- or 5-methyl sulfone, Z-hydroxy-napthalene-4- or 6- or 7-methyl sulfone, 1-phenyl-3-methyl-5- pyrazolone-3'-methyl sulfone, 1-phenyl-3-methyl-5-pyrazolone-4-methyl sulfone and l-acetoacetylaminobenzene-3- or 4-methyl sulfone.

The coupling of the diazo compounds to be used with the coupling-components can be carried out by the usual known methods, advantageously in an alkaline medium, for example, a medium rendered alkaline with an alkali carbonate or an alkali hydroxide. After the coupling reaction the dyestufis can easily be separated from the coupling mixture by filtration for the tion, since they are only slightly soluble in water. They are advantageously used in the form of filter cakes without intermediate drying. In some cases it is also possible to carry out the treatment with the agent yielding cobalt directly in the coupling mixture, that is to say, without any intermediate separation.

The treatment with an agent yielding cobalt is carried out in the present process in such manner that a cobaltiferpurpose of metallizatreatment with the agent yielding cobalt in a weakly acid to alkaline medium. Accordingly, there are especially suitable for the present process those cobalt compounds which are stable in alkaline media such, for example, as complex cobalt compounds of aliphatic dicarboxylic acids or hydroxy-carboxylic acids. As examples of aliphatic dicarboxylic acids and hydroxycarboxylic acids there may be mentioned, among others oxalic acid, lactic acid, glycollic acid, citric acid and especially tartaric acid. As agents yielding cobalt there can also be used with advantage in the present process simple cobalt salts such as cobalt sulfate or cobalt acetate, and also cobalt hydroxide.

The conversion of the dyestuffs into the complex cobalt compounds is advantageously carried out with the aid of heat, under atmospheric or superatmospheric pressure,

and if desired in the presence of suitable additions, for example, in the presence of salts of organic acids, bases, or organic solvents or other agents assisting the formation of complexes.

In a special form of the process there is used as starting material a mixture of difierent metallizable monoazodyestuifs, each of which corresponds to the general definition given above. The treatment with the agent yielding cobalt is carried out in this case also in such manner that the resulting cobaltiferous dyestuffs contain less than one atom of cobalt in complex union per molecule of monoazodyestuff;

The new cobaltiferous dyestuffs of this invention are cobalt compounds, containing less than one atom of cobalt bound in complex union per molecule of dyestuff, and advantageously one atom of cobalt bound in complex union to substantially two molecules of monoazo-dyestuifs free from sulfonic and carboxylic acid groups and corresponding to the general formula (1)11 Ri- -N-Rz in which R1 represents a benzene radical bound to the azo linkage in ortho-position relatively to the hydroxyl group, and R2 represents the radical of a coupling component capable of coupling in a position vicinal to a hydroxyl group and which coupling component contains an aromatic radical, and in which one of the radicals R1 and R2 contains an aromatically bound methyl sulfone, group.

These complex cobalt compounds are soluble in water and in weakly acid aqueous media and are indeed more soluble than the dyestuffs used for making them. They are suitable for dyeing or printing a very wide variety of materials, above all for dyeing animal materials, such as silk, leather and especially wool, but also for dyeing or printing synthetic fibers of superpolyamides or superpolyurethanes. They are suitable above all for dyeing from weakly alkaline or neutral to weakly acid, for example, acetic acid, baths. The wool dyeings so produced are dis tinguished by their level character and good properties of wet fastness, good fastness to decatizing and carbonizing and very good fastness to light.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 18.7 parts of Z-amino-lhydroxybenzene-4-methylsulfone are dissolved in 100 parts of water and 23.4 parts of hydrochloric acid of 30 per cent. strength, and diazotized at -5 C. by means of an aqueous solution of 6.9 parts of sodium nitrite. The diazo suspension is neutralized with sodium carbonate, and poured at 10l2 C.

into a solution of 18 parts of 1-phenyl-3-methyl-5-pyrazolone in 200 parts of water and 13.3 parts of sodium hydroxide solution of 30 per cent. strength. Coupling proceeds very rapidly. The dyestuif formed precipitates al- 5 most completely. It is filtered off, stirred with 300 parts of water, and dissolved by the addition of 26.6 parts of sodium hydroxide solution of 30 per cent. strength. The solution is mixed at ESQ-85 C. with a solution of 16 parts of crystalline cobalt sulfate (CoSO4.7I-I2O) in 100 parts of water, stirred for 30 minutes at that temperature, and the whole is then filtered. The filtrate is evaporated in vacuo. The cobaltiferous dyestufi' so obtained is a water-.

soluble brown powder, which dissolves in concentrated sulfuric acid with an orange-yellow coloration and dyes wool from a neutral or acetic acid bath yellow-brown tints having good properties of fastness.

In the following table are given a few further complex metal compounds which can be made by the process of this example. In all cases cobalt is the metal forming the complex. In column I are given the diazo-components and in column II the coupling components, and in column III are given the tints of the dyeings obtainable by dyeing 100 parts of wool with 2 parts of the cobalt compound from a neutral or acetic acid bath.

I II III 1. 2-Amino-1-hydroxy-ben- Z-hydroxyhaphthalene. reddish borzene-4-methyl sulfone. deaux. 6-bromo-2-hydroxybordeaux.

naphthalene. 5:8-dichloro-1-hydroxybluish bornaphthalene. deaux. aeetoacetylamino-benyellow.

zene. 1-(4-chlorophenyl)-3- brown yelmethyl-5-pyrazolone. low. 6... ...do l-acetoacetylamino-Z- yellow.

chlorobenzene. I 7... l-acetylamino-7-hygreyish viodroxynaphthalene. let. 8. l-phenyl-S-methyl-S-pyb r 0 w n or razolone-lniethylstilange. toner 9. 1-pheny1-3-methyl5-pyb r o w n i s h tazolone-3-suli0nic yellow.

acid amide.v

10. Z-amino-l-hydroxy-ben- 1-pl1enyl-3- ethyl-fi-pyorange.

zene-5-methyl sulfone. razolone.

11.. acetoacetylamino-benreddish yelzene. low.

12- .---do B-naphthol bordeaux.

13- 2-amino-1-hydroxy-ben- Z-hydroxynaphthalene- Do.

zene-i-sulfonic acid 7-methyl sulfone. methylamide.

14- Z-amino-l-hydroxy-ben- 5:8-dichloro-1-hydroxyviolet.

zene-5-methyl-sulfone. naphthalene.

15.. do l-(4-ehlorophenyl)-3- orange.

methyl-5-pyrazolone.

16- 4-nitro-2-amino-1-hy- 1-phenyl-3-methyl-5-pyb r o w n i s h droxybenzene. razolone-4-methy1- yellow.

snltone.

17.. 5-nitro-2-amino-1-l1y- .---.do r e d d i s h droxybenzene. brown.

18- 4-chloro-2-amino-1-hy- ...do b r o w n i s h droxybenzene. 7 yellow.

19. 2-amino-1-l1ydroxybenl-acetoacetyl-aminoyellow.

zene-t-sulfonic acid benzene-i-rnethyl sulamide. tone.

20. 2-amino-l-hydroxy-ben- -....do b r o w n i s h zenet-sultonic acid yellow. anilide.

21 3-amino-4-hydroxy-ace- ..do Do.

tophenone.

22. 4-nitro-2-amino-1-hy- ..-do Do.

droxybenzene.

Example 2 19.95 parts of the dyestuff obtained from diazotized 2- amino-l-hydroxybenzene-4-methyl sulfone and l-acetyl- I amino-7-hydroxynaphthalene, and 20.3 parts of-the dyestnfl? obtained from diazotized z-amino-l-hydr'oxybenzene- 4-methyl sulfone and l-(4'-chlorophenyl)-3-methy1-5- pyrazolone are dissolved together in 2000 parts of water with the addition of 8 parts of sodium hydroxide, and mixed at 80 C. with 100 parts of a cobalt sulfate solution having a cobalt content of 3.25 per cent. After stirring for about /2 hour at 80 C. the metallization is finished. The cobalt complex is precipitated by the addition of sodium chloride. When dry it is a brown powder which dissolves in water with a brown coloration and in concentrated sulfuric acid with an orange coloration, and dyes wool from a weakly alkaline bath or a neutral or acid bath full brown tints having an excellent fastness to washing, decatizing and carbonizing.

Dyestufis having similar properties are obtained by using instead of the monoazo-dyestuffs mentioned in the preceding paragraph the dyestuffs given in the following table, and otherwise proceeding in an analogous manner. In columns A and B are given the two ortho:ortho'-dihydroxymonoazo-dyestufls bound in complex union to cobalt, and in column C are given the tints obtained by dyeing wool from an acetic acid or neutral bath.

A B C 1 2-Amino-l-hydroxy-b en- Z-amino-I-hydroxy-benbordeaux.

zene 4 methylsulfone zene 4 methylsulfone 2-hydroxynaphtha- 5 :8-dichloro l-hylene. droxynaphthalene. 2 2-amino-l-hydroxy-bendo reddish zene 4 methylsultone brown.

- 1 acetoacetylami no-2-chlorobenzene. 3-.." 4 -nitro 2- amino 1 -hy- 2-amino -1 -hydroxybenbrownish droxybenzene 1 zene 4 methylsulfone yellow.

phenyl 3 methyl 5 l acetoacetylamr pyrazolone 4 methyl no-2-chlorobenzene.

one.

Example 3 0.5 part of the cobaltiferous dyestuif obtained as described in Example 1 is dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added, and 100 parts of well wetted wool are entered at 40-50 C. into the resulting dyebath. 3 parts of acetic acid of 40 per cent. strength are then added, the bath is raised to the boil in the course of /2 hour, and dyeing is carried on for /1 hour at the boil. Finally the wool is rinsed with cold Water and dried. There is obtained a level brownjyellow dyeing having good properties of fastness to washing and light.

Practically the same dyeing is obtained if no acetic acid is added to the dyebath.

What is claimed is:

1. A complex cobalt compound containing one atom of cobalt bound in complex union with substantially to monoazo dyestufis free from sulfonic acid and carboxylic acid groups, which correspond to the formula I l1N=NRz wherein R1 represents a benzene radical bound to the azo-linkage in ortho-position relatively to the hydroxyl group, and R2 represents a radical selected from the group consisting of a hydroxynaphthalene radical bound to the azo-linkage in a position vicinal to the hydroxy group, a l-phenyl-S-pyrazolone radical bound to the azo-linkage in 4-position, and the radical of a B-ketocarboxylic acid arylide bound to the azo-linkage in a-position, and wherein at least one of the radicals R1 and R2 contains an aromatically bound methyl sulfone group.

2. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufl free from sulfonic acid and carboxylic acid groups, which corresponds to the formula wherein R1 represents a benzene radical bound to the a'zolinkage in ortho-position relatively to the hydroxyl group, and R2 represents a radical selected from the group consisting of a hydroxynaphthalene radical bound to the azo linkage in a position vicinal to the hydroxy group, a l-phenyl-5-pyrazolone radical bound to the azo-linkage in 4-position, and the radical of a ,B-ketocarboxylic acid arylide bound to the azo linkage in a-position.

3. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dycstufi free from sulfonic acid and carboxylic acid groups, which corresponds to the formula 0 O-CH:

SOICHS wherein R1 represents a benzene radical bound to the azo linkage in ortho-position relatively to the hydroxyl group.

4. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestuff free from sulfonic acid and carboxylic acid groups, which corresponds to the formula COOH:

wherein X represents a member selected from the group consisting of a nitro group, a chlorine atom, a sulfonic acid amide group, and a COCH3 group.

5. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufi free from sulfonic acid and carboxylic acid groups, which corresponds to the formula SOa-CHs wherein R2 represents a 2-hydroxynaphthalene radical bound to the azo-linkage in l-position.

6. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufi free from sulfonic acid and carboxylic acid groups, which corresponds to the wherein R3 represents a benzene radical.

7. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufi free from sulfonic acid and carboxylic acid groups, which corresponds to the formula 8 :03: wherein R3 represents a benzene radical.

8. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufi corresponding to the formula I COCH:

SOzOHS 9. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestuft' corresponding to the formula OH HO I -Q N=N-O l S 2C Ha iu. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestuff corresponding to the formula OH H I I S 62 C Ha X wherein X represents a member selected from the group consisting of a hydrogen and a bromine atom, and Y represents a member selected from the group consisting of an 'acetylamino group and a hydrogen atom, at least one of the two symbols X and Y standing for hydrogen.

11. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two 7 molecules of a monoazo dyestufi corresponding to the molecules of a monoazo dyestufi corresponding to the formula COCHa l SO2CH3 00011:

13. The complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of the monoazo dyestufi of the formula 14'. The complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of the monoazo dyestufi of the formula OH 7 HO (I11 m SOaCHa C1 15. The complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of the monoazo dyestulf of the formula OH HCI) SOzCH:

16. The complex cobalt compound containing one atom of cobalt bound in complex union tosubstantially two molecules of the monoazo dyestufi of the formula OH 3T0 I SOzCHs 17. The complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of the monoazo dyestuff of the formula OzCHa References Cited in the file of this patent UNITED STATES PATENTS Felix et a1. Dec. 9, 1947 Schetty May 1, 1951

Claims

1. A COMPLEX COBALT COMPOUND CONTAINING ONE ATOM OF COBALT BOUND IN COMPLEX UNION WITH SUBSTANTIALLY TO MONOAZO DYESTUFFS FREE FROM SULFONIC ACID AND CARBOXYLIC ACID GROUPS, WHICH CORRESPOND TO THE FORMULA